Vegetable oil-based coating and method for application

ABSTRACT

A method of applying a urethane material to a vehicle substrate that includes the steps of: providing a vehicle substrate; and applying a urethane material to the vehicle substrate where the urethane material typically includes the reaction product of an A-side that includes an isocyanate and a B-side that typically includes a blown soy oil, at least one polyol at least partially derived from petroleum, and a cross-linker. A vehicle composite that typically includes the vehicle substrate and the urethane material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/569,457, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Sep. 29, 2009, thedisclosure of which is hereby incorporated by reference in its entirety.U.S. patent application Ser. No. 12/569,457 is a continuation of U.S.patent application Ser. No. 11/042,980, now issued as U.S. Pat. No.7,595,094, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Jan. 25, 2005, thedisclosure of which is hereby incorporated by reference in its entirety.U.S. patent application Ser. No. 11/042,980, now issued as U.S. Pat. No.7,595,094, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Jan. 25, 2005, is adivisional of U.S. patent application Ser. No. 10/004,733, now issued asU.S. Pat. No. 6,979,477, entitled VEGETABLE OIL-BASED COATING AND METHODFOR APPLICATION, by Thomas M. Kurth et al., filed Dec. 4, 2001, which ishereby incorporated by reference in its entirety.

U.S. patent application Ser. No. 10/004,733, now issued as U.S. Pat. No.6,979,477, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Dec. 4, 2001, is acontinuation-in-part of U.S. patent application Ser. No. 09/646,356, nowU.S. Pat. No. 6,465,569, entitled PLASTIC MATERIAL, by Thomas M. Kurth,filed Sep. 14, 2000, which is hereby incorporated by reference in itsentirety. U.S. patent application Ser. No. 09/646,356, now U.S. Pat. No.6,465,569, is the National Stage of International Application No.PCT/US99/21511, filed on Sep. 17, 1999, which is hereby incorporated byreference in its entirety and which is a continuation-in-part of U.S.patent application Ser. No. 09/154,340, now U.S. Pat. No. 6,180,686,entitled IMPROVED CELLULAR PLASTIC MATERIAL filed on Sep. 17, 1998,which is hereby incorporated by reference in its entirety.

U.S. patent application Ser. No. 10/004,733, now issued as U.S. Pat. No.6,979,477, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Dec. 4, 2001, is also acontinuation-in-part of U.S. patent application Ser. No. 09/944,212,entitled TRANSESTERIFIED POLYOL HAVING SELECTABLE AND INCREASEDFUNCTIONALITY AND URETHANE MATERIAL PRODUCTS FORMED USING THE POLYOL, byThomas M. Kurth et al., filed on Aug. 31, 2001, which is herebyincorporated by reference in its entirety and which claims the benefitof and priority to: (1) U.S. Provisional Patent Application Ser. No.60/230,463, entitled TRANSESTERIFIED POLYOL HAVING SELECTABLE ANDINCREASED FUNCTIONALITY AND URETHANE PRODUCTS FORMED USING THE POLYOL,by Thomas M. Kurth et al., filed on Sep. 6, 2000; (2) U.S. ProvisionalPatent Application Ser. No. 60/239,161, entitled TRANSESTERIFIED POLYOLHAVING SELECTABLE AND INCREASED FUNCTIONALITY AND URETHANE PRODUCTSFORMED USING THE POLYOL, by Thomas M. Kurth et al., filed on Oct. 10,2000; and (3) U.S. Provisional Patent Application Ser. No. 60/251,068,entitled TRANSESTERIFIED POLYOL HAVING SELECTABLE AND INCREASEDFUNCTIONALITY AND URETHANE PRODUCTS FORMED USING THE POLYOL, by ThomasM. Kurth et al., filed on Dec. 4, 2000. The disclosures of each of theabove provisional applications, U.S. Patent Application Ser. Nos.60/230,463; 60/239,161; and 60/251,068 are each incorporated byreference in their entirety.

U.S. patent application Ser. No. 10/004,733, now issued as U.S. Pat. No.6,979,477, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Dec. 4, 2001, is also acontinuation-in-part of U.S. patent application Ser. No. 09/974,301, nowissued as U.S. Pat. No. 6,962,636, entitled METHOD OF PRODUCINGBIO-BASED CARPET MATERIAL, by Thomas M. Kurth et al., filed on Oct. 10,2001, which is hereby incorporated by reference in its entirety andwhich claims the benefit of and priority to: (1) U.S. Provisional PatentApplication Ser. No. 60/239,161, entitled TRANSESTERIFIED POLYOL HAVINGSELECTABLE AND INCREASED FUNCTIONALITY AND URETHANE PRODUCTS FORMEDUSING THE POLYOL, by Thomas M. Kurth et al., filed on Oct. 10, 2000; and(2) U.S. Provisional Patent Application Ser. No. 60/251,068, entitledTRANSESTERIFIED POLYOL HAVING SELECTABLE AND INCREASED FUNCTIONALITY ANDURETHANE PRODUCTS FORMED USING THE POLYOL, by Thomas M. Kurth et al.,filed on Dec. 4, 2000.

U.S. patent application Ser. No. 10/004,733, now issued as U.S. Pat. No.6,979,477, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Dec. 4, 2001, is also acontinuation-in-part of U.S. patent application Ser. No. 09/974,303, nowabandoned, entitled OXYLATED VEGETABLE-BASED POLYOL HAVING INCREASEDFUNCTIONALITY AND URETHANE MATERIAL FORMED USING THE POLYOL, by ThomasM. Kurth et al., filed on Oct. 10, 2001, which is hereby incorporated byreference in its entirety.

U.S. patent application Ser. No. 10/004,733, now issued as U.S. Pat. No.6,979,477, entitled VEGETABLE OIL-BASED COATING AND METHOD FORAPPLICATION, by Thomas M. Kurth et al., filed Dec. 4, 2001, also claimsthe benefit of U.S. Provisional Application Ser. No. 60/251,068,entitled TRANSESTERIFIED POLYOL HAVING SELECTABLE AND INCREASEDFUNCTIONALITY AND URETHANE PRODUCTS FORMED USING THE POLYOL, by ThomasM. Kurth et al., filed on Dec. 4, 2000.

BACKGROUND OF THE INVENTION

Because of their widely ranging mechanical properties and their abilityto be relatively easily machined and formed, plastic foams andelastomers have found wide use in a multitude of industrial and consumerapplications. In particular, urethane materials, such as foams andelastomers, have been found to be well suited for many applications.Vehicles, for instance, contain a number of components, such as cabininterior parts or cargo lay areas that are comprised of urethane foamsand elastomers. Urethane foams are also used as carpet backing. Suchurethane foams are typically categorized as flexible, semi-rigid, orrigid foams with flexible foams generally being softer, less dense, morepliable, and more subject to structural rebound subsequent to loadingthan rigid foams.

The production of urethane foams and elastomers are well known in theart. Urethanes are formed when isocyanate (NCO) groups react withhydroxyl (OH) groups. The most common method of urethane production isvia the reaction of a polyol and an isocyanate, which forms the backboneurethane group. A cross-linking agent and/or chain extender may also beadded. Depending on the desired qualities of the final urethane product,the precise formulation may be varied. Variables in the formulationinclude the type and amounts of each of the reactants and additives.

In the case of a urethane foam, a blowing agent is added to cause gas orvapor to be evolved during the reaction. The blowing agent is oneelement that assists in creating the size of the void cells in the finalfoam, and commonly is a solvent with a relatively low boiling point ofwater. A low boiling solvent evaporates as heat is produced during theexothermic isocyanate/polyol reaction to form vapor bubbles. If water isused as a blowing agent, a reaction occurs between the water and theisocyanate group to form an amine and carbon dioxide (CO₂) gas in theform of bubbles. In either case, as the reaction proceeds and thematerial solidifies, the vapor or gas bubbles are locked into place toform void cells. Final urethane foam density and rigidity may becontrolled by varying the amount or type of blowing agent used.

A cross-linking agent is often used to promote chemical cross-linking toresult in a structured final urethane product. The particular type andamount of cross-linking agent used will determine final urethaneproperties such as elongation, tensile strength, tightness of cellstructure, tear resistance, and hardness. Generally, the degree ofcross-linking that occurs correlates to the flexibility of the finalfoam product. Relatively low molecular weight compounds with greaterthan single functionality are found to be useful as cross-linkingagents.

Catalysts may also be added to control reaction times and to effectfinal product qualities. The catalysts generally effect the speed of thereaction. In this respect, the catalyst interplays with the blowingagent to effect the final product density. Preferably, for foam urethaneproduction, the reaction should proceed at a rate such that maximum gasor vapor evolution coincides with the hardening of the reaction mass.The catalyst may also effect the timing or speed of curing so that aurethane foam may be produced in a matter of minutes instead of hours.

Polyols currently used in the production of urethanes are petrochemicalsbeing generally derived from propylene or ethylene oxides. Polyesterpolyols and polyether polyols are the most common polyols used inurethane production. For flexible foams, polyester or polyether polyolswith molecular weights greater than 2,500, are generally used. Forsemi-rigid foams, polyester or polyether polyols with molecular weightsof 2,000 to 6,000 are generally used, while for rigid foams, shorterchain polyols with molecular weights of 200 to 4,000 are generally used.There is a very wide variety of polyester and polyether polyolsavailable for use, with particular polyols being used to engineer andproduce a particular urethane elastomer or foam having desiredparticular final toughness, durability, density, flexibility,compression set ratios and modulus, and hardness qualities. Generally,higher molecular weight polyols and lower functionality polyols tend toproduce more flexible foams than do lower molecular weight polyols andhigher functionality polyols. In order to eliminate the need to produce,store, and use different polyols, it would be advantageous to have asingle, versatile, renewable component that was capable of being used tocreate final urethane foams of widely varying qualities.

Currently, one method employed to increase the reactivity of petroleumbased polyols includes propoxylation or ethoxylation. When propoxylationor ethoxylation is done on conventional petroleum based polyols, currentindustry practice is to employ about 70% propylene oxide by weight ofthe total weight of the polyol and propylene oxide is required tocomplete the reaction. Due to the large amount of alkyloxide typicallyused, the reaction of the alkyloxide and the petroleum based polyol isextremely exothermic and alkyloxides can be very expensive to use,especially in such high volumes. The exothermic nature of the reactionrequires numerous safety precautions be undertaken when the process isconducted on an industrial scale.

Use of petrochemicals such as, polyester or polyether polyols isdisadvantageous for a variety of reasons. As petrochemicals areultimately derived from petroleum, they are a non-renewable resource.The production of a polyol requires a great deal of energy, as oil mustbe drilled, extracted from the ground, transported to refineries,refined, and otherwise processed to yield the polyol. These requiredefforts add to the cost of polyols and to the disadvantageousenvironmental effects of its production. Also, the price of polyolstends to be somewhat unpredictable. Their price tends to fluctuate basedon the fluctuating price of petroleum.

Also, as the consuming public becomes more aware of environmentalissues, there are distinct marketing disadvantages to petrochemicalbased products. Consumer demand for “greener” products continues togrow. The term “bio-based” or “greener” polyols for the purpose of thisapplication is meant to be broadly interpreted to mean all polyols notderived exclusively from non-renewable resources. Petroleum andbio-based copolymers are also encompassed by the term “bio-based”. As aresult, it would be most advantageous to replace polyester or polyetherpolyols, as used in the production of urethane elastomers and foams,with more versatile, renewable, less costly, and more environmentallyfriendly components.

The difficulties in the past that occurred due to the use of vegetableoil as the polyols to produce a urethane product include the inabilityto regulate the functionality of the polyol resulting in variations inurethane product where the industry demands relatively strictspecifications be met and the fact that urethane products, in the past,outperformed vegetable oil based products in quality tests, such ascarpet backing pull tests.

An unresolved need therefore exists for an improved functionality,vegetable oil based polyol of increased and selectable functionality foruse in manufacturing urethane materials such as, elastomers and foams.Also needed is a method of producing such urethane materials, inparticular, carpet materials using the improved functionality, vegetableoil based polyol based on a reaction between isocyanates alone or as aprepolymer, in combination with the improved functionality polyol or ablend of the improved functionality polyol and other polyols includingpetrochemical based polyols. The products and methods of the presentinvention are particularly desirable because they relate to relativelyinexpensive, versatile, renewable, environmentally friendly materialssuch as, vegetable oil, blown soy oil, or transesterified vegetable oilthat forms a polyol of increased and selectable functionality that canbe a replacement for soy or petroleum based polyether or polyesterpolyols typically employed.

SUMMARY OF THE INVENTION

One aspect of the present invention includes a method of coating asubstrate with a material by providing a substrate, an A-side reactantcomprising an isocyanate, and a B-side reactant having an esterifiedpolyol and a catalyst wherein the esterified polyol includes thereaction product of a first polyol and a vegetable oil and the firstpolyol comprises the reaction product of a first multifunctionalcompound and a second multifunctional compound, directing the A-side andB-side reactants toward the substrate, and applying the A-side andB-side reactants to the substrate to form a urethane material thatcontacts the substrate.

Another embodiment of the present invention includes a method of coatinga substrate with a material by providing a substrate; an applicatorhaving an A-side intake, an A-side outlet, a B-side intake, a B-sideoutlet, and a nozzle head; an A-side reactant including an isocyanate;and a B-side reactant where the B-side reactant includes a vegetableoil, a cross-linking agent having a multifunctional alcohol, and acatalyst, and passing the A-side reactant through the A-side intake ofthe applicator and the B-side reactant through the B-side intake of theapplicator such that the A-side and the B-side reactants pass throughthe applicator nozzle head and contact the substrate to form a urethanecoating.

Yet another embodiment of the present invention includes a boat hullcomposite having a boat hull and a urethane material where the urethanematerial includes the reaction product of an A-side including anisocyanate and a B-side including an esterified polyol and a catalystwhere the esterified polyol includes the reaction product of a firstpolyol and a vegetable oil and the first polyol includes the reactionproduct of a first multifunctional compound and a second multifunctionalcompound and where the urethane material at least partially covers theboat hull.

Still another embodiment of the present invention includes a boat hullcomposite including a boat hull, a urethane material at least partiallycovering the boat hull where the urethane material includes anisocyanate and a B-side reactant wherein the B-side includes a vegetableoil, a cross-linking agent, and a catalyst.

In another embodiment of the present invention, a building materialcomposite includes a building substrate at least partially combined witha urethane material where the urethane material includes the reactionproduct of an A-side having an isocyanate and a B-side having anesterified polyol and a catalyst, where the esterified polyol includesthe reaction product of a first polyol and a vegetable oil and the firstpolyol includes the reaction product of a first multifunctional compoundand a second multifunctional compound.

In yet another embodiment of the present invention, a building materialincludes a building substrate at least partially combined with aurethane material where the urethane material includes the reactionproduct of an A-side having an isocyanate and a B-side where the B-sidehas a vegetable oil, a cross-linking agent, and a catalyst.

Still another embodiment of the present invention includes a method ofmanufacturing a carpet material by providing a carpet substrate, anapplicator having an A-side intake, a B-side intake, and at least onenozzle head, an A-side having an isocyanate, and a B-side having anesterified polyol and a catalyst where the esterified polyol includesthe reaction product of a first polyol and a vegetable oil and the firstpolyol includes the reaction product of a first multifunctional compoundand a second multifunctional compound.

In yet another embodiment of the present invention, a method of coatinga substrate with a material includes: providing a substrate; a sprayapplicator having an A-side inlet, a B-side inlet, and a sprayer headincluding an A-side outlet and a B-side outlet; an A-side reactanthaving an isocyanate; and a B-side reactant having an esterified polyol,a petroleum based polyol, and a catalyst where the esterified polyolincludes the reaction product of a first polyol and a vegetable oil, thefirst polyol includes the reaction product of a first multifunctionalcompound and a second multifunctional compound, directing the sprayapplicator toward the substrate, passing the A-side reactant through theA-side intake of the applicator and the B-side reactant through theB-side intake of the applicator, and passing the A-side reactant and theB-side reactant through the sprayer head such that the A-side and B-sidereactants react and contact the substrate material.

In yet another embodiment of the present invention, a method of coatinga substrate with a material includes providing a substrate; a sprayapplicator having an A-side inlet, a B-side inlet, and a sprayer headincluding an A-side outlet and a B-side outlet; an A-side reactanthaving an isocyanate; and a B-side reactant having a vegetable oil, apetroleum based polyol, a cross-linker, and a catalyst, directing thespray applicator toward the substrate, passing the A-side reactantthrough the A-side intake of the applicator and the B-side reactantthrough the B-side intake of the applicator, and passing the A-sidereactant and the B-side reactant through the sprayer head such that theA-side and B-side reactants react and contact the substrate material.

In still another embodiment of the present invention, a vehiclecomponent liner composite includes a vehicle component and a urethanematerial where the urethane material includes the reaction product of anA-side having an isocyanate and a B-side having an esterified polyol anda catalyst where the esterified polyol includes the reaction product ofa first polyol and a vegetable oil and the first polyol includes thereaction product of a first multifunctional compound and a secondmultifunctional compound and where the urethane material at leastpartially covers the boat hull.

In another embodiment of the present invention, a vehicle componentliner composite includes a vehicle component and a urethane material atleast partially covering the boat hull where the urethane materialincludes an A-side having an isocyanate and a B-side wherein the B-sideincludes a vegetable oil, a cross-linking agent, and a catalyst.

Yet another aspect of the present invention is generally directed towarda method of applying a urethane material to a vehicle substrate thatincludes the steps of: providing a vehicle substrate and applying aurethane material to the vehicle substrate where the urethane materialtypically includes the reaction product of an A-side that includes anisocyanate and a B-side that typically includes a blown soy oil, atleast one polyol at least partially derived from petroleum, and across-linker.

These and other features, advantages and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification, claims and appendeddrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an enlarged elevated view of an applicator of one embodimentof the present invention;

FIG. 2 is a section of an interior of a boat hull, which is shown havinga urethane material applied thereto in accordance with an embodiment ofthe present invention;

FIG. 3 shows the interior of a vehicle cargo area having a urethanematerial applied thereto in accordance with an embodiment of the presentinvention;

FIG. 4 show the exterior roof portion of a building material having aurethane material applied thereto in accordance with an embodiment ofthe present invention;

FIG. 5 is a second of housing material, which is shown having a urethanematerial applied thereto in accordance with the present invention;

FIG. 6 shows a carpet material having a urethane material appliedthereto in accordance with an embodiment of the present invention; and

FIG. 7 shows a carpet material having a urethane material appliedthereto in accordance with an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

New methods to apply to a vegetable oil based urethane material to anysubstrate and composition made in accordance with the methods have beendeveloped. The vegetable oil based urethane material may comprise thevegetable oil based material produced according to the teachings of U.S.Pat. No. 6,180,686 and WO 00/15684, the disclosures of which are herebyincorporated by reference. These two patent publications teach abio-based urethane material that is the reaction product of an A-sideand a B-side where the A-side includes any isocyanate, preferably adiisocyanate, (a triisocyanate or other suitable isocyanates can be usedin any A-side formulation when desirable) and the B-side includes across-linker, preferably a multi-functional alcohol, a vegetable oil,preferably a blown vegetable oil, and a catalyst.

The vegetable oil based urethane material may also be produced from atransesterified vegetable oil based polyol, which includes the reactionproduct of a multifunctional alcohol and a multifunctional component,subsequently reacted with a vegetable oil. The transesterified polyol ispreferably produced using a two-stage process. In the first step in thetwo-stage transesterification process, glycerin, a suitablemultifunctional alcohol, or other suitable multifunctional compound ispreferably heated to about 230° F., and advantageously also stirred;however, a catalyst may be used instead of or in addition to heat. Next,a multifunctional component having at least two hydroxyl groups,preferably including a saccharide compound, typically a monosaccharide,disaccharide, a polysaccharide, sugar alcohol, cane sugar, honey, ormixture thereof, is slowly introduced into the glycerin until saturated.Currently, the preferred saccharide components are fructose and canesugar. Cane sugar provides greater tensile strength and fructoseprovides greater elongation of the carbon chain of the polyol.Preferably, 2 parts of the saccharide compound are added to 1 part ofthe multifunctional alcohol, by weight. Glycerin is a carrier for thesaccharide compound component, although it does add some functionalhydroxyl groups. The saccharide component is slowly added until noadditional saccharide component can be added to the glycerin solution.

It is believed that the multifunctional alcohol and the saccharidecomponent undergo an initial transesterification to form new esterproducts (precursors). As such, the functionality of the new polyol isselectable. The greater the functionality of the alcohol, the greaterthe functionality of the final new polyol.

Next, from about 200 to 300 grams (experimental amount) of vegetableoil, preferably soy oil, and most preferably blown soy oil, is heated toat least about 180° F. However, the temperature may be any temperaturefrom about 180° F. until the oil is damaged. Blown soy oil providessuperior results to regular vegetable oil; however, any vegetable oil orblown vegetable oil will work. Other vegetable oils that may be utilizedin the present invention include, but should not be limited to, palmoil, safflower oil, sunflower oil, canola oil, rapeseed oil, cottonseedoil, linseed, and coconut oil. When these vegetable oils are used, theytoo are preferably blown. However, the vegetable oils may be crudevegetable oils or crude vegetable oils that have had the soap stock andwax compound in the crude oil removed.

Once the blown soy oil has been heated, it is slowly reacted with theheated glycerin/saccharide ester, the first transesterification reactionproduct. The vegetable oil and the first transesterification productundergo a second transesterification reaction that increases thefunctionality of the resulting polyol. Lowering the amount of thesaccharide component added to the vegetable oil lowers the number offunctional groups available to be cross-linked with an isocyanate groupwhen the polyol produced using the two-stage transesterification processoutlined above is used to create a urethane product. In this manner,functionality of the final polyol produced by the transesterificationprocess of the present invention may be regulated and engineered.Therefore, more rigid urethane products are formed using a polyolproduced by the present invention by using increased amounts of asaccharide component. In addition, as discussed above, the higherfunctionality of the multifunctional alcohol may also increase thefunctionality of the urethane products formed using the new polyol.

Moreover, it has been contemplated that the above describedtransesterification process may be performed on crude or non-blownvegetable (soy) oil prior to blowing the vegetable (soy) oil to form apre-transesterified vegetable (soy) oil. The pre-transesterifiedvegetable (soy) oil may then be blown, as known, to increase itsfunctionality. Thereafter, the transesterification process discussedabove may optionally be carried out again on the blownpre-transesterified vegetable (soy) oil.

A transesterification catalyst such as tetra-2-ethylhexyl titonate,which is marketed by DuPont® as Tyzor® TOT, may be used, instead of orin addition to heat. Also, known acids and other transesterificationcatalysts known to those of ordinary skill may also be used.

Also, polyols having increased functionality can not only be made by thetransesterification process discussed above alone, but a furtherincrease in functionality of the vegetable oil based polyol may also beachieved by propoxylation, butyoxylation, or ethoxylation. Applicantsbelieve that the addition of propylene oxide (propoxylation), ethyleneoxide (ethoxylation), butylene oxide, (butyloxylation), or any otherknown alkene oxides to a vegetable oil, a crude vegetable oil, a blownvegetable oil, the reaction product of the saccharide (multifunctionalcompound) and the multifunctional alcohol, or the final vegetable oilbased, transesterified polyol produced according to thetransesterification process discussed above will further increase thefunctionality of the polyol thereby formed.

Also, polyols having increased functionality can not only be made by thetransesterification process discussed above alone, but a furtherincrease in functionality of a vegetable oil based polyol may also beachieved by oxylation (propoxylation, butyoxylation, or ethoxylation).The addition of propylene oxide (propoxylation), ethylene oxide(ethoxylation), butylene oxide, (butyloxylation), or any other knownalkene oxides to a vegetable oil, a crude vegetable oil, a blownvegetable oil, the reaction product of the saccharide (multifunctionalcompound) and the multifunctional alcohol, or the final vegetable oilbased, transesterified polyol produced according to thetransesterification process discussed above will further increase thefunctionality of the polyol thereby formed.

Applicants currently believe that bio-based oxylation substances, suchas, tetrahydrofuran (THF), tetrahydrofurfuryl, tetrahydrofurfural, andfurfural derivatives as well as tetrahydrofurfuryl alcohol may be usedinstead of or in addition to alkyloxides in the present invention.

Moreover, Applicants believe that any substance containing an activehydrogen may be oxylated to any desired degree and subsequentlytransesterified. Once transesterified with the vegetable oil, a compoundwhose active hydrogens were not fully oxylated may be further oxylated.Some active hydrogens include OH, SH, NH, chorohydrin, or any acidgroup. Compounds containing these active hydrogens, such as ethylenediamine, may be partially (because it contains more than one activehydrogen) or fully oxylated and then transesterified with themultifunctional alcohol, a crude vegetable oil, a blown vegetable oil,the reaction product of the saccharide (multifunctional compound) andthe multifunctional alcohol, or the final vegetable oil based,transesterified polyol produced according to the transesterificationprocess discussed above will further increase the functionality of thepolyol thereby formed.

When propoxylation or like reactions are done to the vegetable oil orthe transesterified polyol, an initiator/catalyst is typically employedto start and, throughout the reaction, to maintain the reaction of thepropylene oxide and the vegetable oil to the transesterified polyol. Theresulting reaction is an exothermic reaction. Initiators/catalysts thatmay be employed in the propoxylation, ethyloxylation, or butyloxylationreaction include triethylamine, trimethylamine, or other suitable aminesas well as potassium hydroxide or other suitable metal catalyst.

Significantly, while about 70% by weight of alkyloxides is typicallyused to fully oxylate a petroleum based polyol, when oxylation of crude,blown, or transesterified vegetable based polyols is conducted, onlyabout 5% to about 10% of the oxylation compound is necessary. As aresult, Applicants have found that, in experimental amounts, thereaction is not nearly as exothermic as a “typical” oxylation reactionusing a petroleum based product. As a result, Applicants believe thiswill be a significant safety benefit when done at production scale.Applicants have suprisingly found that adding heat to the oxylationreaction employing a vegetable based polyol is preferred. On anindustrial scale, this may provide the additional benefit of regulatingreaction time. Obviously, since significantly less oxylation rawmaterial is used when oxylation is done to the vegetable based polyol ofthe present invention, significant cost savings result as well.Additionally and probably most significantly, oxylation of the vegetablebased polyols of the present invention, either blown or transesterified,results in a vegetable oil based polyol with improved reactive andchemical properties.

In practice, the alkyloxide or bio-based oxylation compound and asuitable catalyst/initiator are added to a vegetable oil, preferably ablown or transesterified vegetable oil and mixed. The resultant mixtureis then heated until the temperature reaches about 100° C. Thetemperature is held at about 100° C. for about one to about two hours.The mixture is then cooled to ambient temperature while pulling a vacuumto remove any excess alkyloxide or bio-based oxylation compound.

The preparation of urethanes is well known in the art. They aregenerally produced by the reaction of petrochemical polyols, eitherpolyester or polyether, with isocyanates. The flexibility or rigidity ofthe foam is dependent on the molecular weight and functionality of thepolyol and isocyanate used.

Polyol based polyurethanes can be prepared when what is known in the artas an A-side reactant is combined with what is known in the art as aB-side reactant. The A-side reactant of the urethane of the presentinvention comprises an isocyanate, typically a diisocyanate such as:4,4′ diphenylmethane diisocyanate; 2,4 diphenylmethane diisocyanate; andmodified diphenylmethane diisocyanate. Typically, a modifieddiphenylmethane diisocyanate is used. Mondur MR Light®, an aromaticpolymeric isocyanate based on diphenylmethane-diisocyanate, and Mondur®MA-2903, a new generation MDI prepolymer, manufactured by Bayer®Corporation, are two specific examples of possible isocyanates that canbe used. It should be understood that mixtures of different isocyanatesmay also be used. The particular isocyanate or isocyanate mixture usedis not essential and can be selected for any given purpose or for anyreason as desired by one of ordinary skill in the art.

The A-side of the reaction may also be a prepolymer isocyanate. Theprepolymer isocyanate is the reaction product of an isocyanate,preferably a diisocyanate, and most preferably some form ofdiphenylmethane diisocyanate (MDI) and a vegetable oil. The vegetableoil can be any of the vegetables discussed previously or any other oilhaving a suitable number of reactive hydroxyl (OH) groups. Soy oil isparticularly advantageous to use. To create the prepolymer diisocyanate,the vegetable oil, the transesterified vegetable oil or a mixture ofvegetable oils and transesterified vegetable oils are mixed and allowedto react until the reaction has ended. There may be some unreactedisocyanate (NCO) groups in the prepolymer. However, the total amount ofactive A-side material has increased through this process. Theprepolymer reaction reduces the cost of the A-side component bydecreasing the amount of isocyanate required and utilizes a greateramount of inexpensive, environmentally friendly vegetable (soy) oil.Alternatively, after the A-side prepolymer is formed, additionalisocyanates may be added.

The conventional petroleum-based B-side material is generally a solutionof a petroleum based polyester or polyether polyol, cross-linking agent,and blowing agent. A catalyst is also generally added to the B-side tocontrol reaction speed and effect final product qualities. As discussedinfra, the use of a petrochemical such as, a polyester or polyetherpolyol is undesirable for a number of reasons.

It has been discovered that urethane materials of high quality can beprepared by substituting the petroleum based polyol in the B-sidepreparation with the increased and selectable functionality polyolproduced by the transesterification process outlined above; or, asdiscussed earlier, a blown vegetable oil, a cross-linker and a catalyst;or any oxylated vegetable oil or oxylated transesterified vegetable oilas discussed herein. Using Applicants' bio-based polyols permitssubstantial regulation of the functionality of the resulting bio-basedpolyol thereby making the polyols produced by Applicants' new processesmore desirable to the industry. Previously, the functionality ofvegetable oil based polyols varied dramatically due to, for example,genetic or environmental reasons.

In addition to the increased and selectable functionality polyolproduced by the processes outlined above, the B-side of the urethanereaction may optionally include a cross-linking agent. Surprisingly, across-linking agent is not required when using the new transesterifiedpolyol to form a urethane product. Typically, a blowing agent and acatalyst are also used in the B-side of the reaction. These componentsare also optional, but are typically used to form urethane product,especially foams.

A currently preferred blown soy oil typically used when forming any ofthe bio-based polyols and urethane materials of the present invention orpracticing the methods of the present invention has the followingcomposition; however, the amounts of each component vary over a widerange. These values are not all inclusive. Amounts of each components ofthe oil vary due to weather conditions, type of seed, soil quality andvarious other environmental conditions:

100% Pure Soybean Oil Air Oxidized Moisture 1.15% Free Fatty Acid 1-6 %,typically ≈ 3% Phosphorous 50-200 ppm Peroxide Value 50-290 Meq/Kg Iron≈6.5 ppm (naturally occurring amount) Hydroxyl Number 42-220 mgKOH/gAcid Value 5-13 mgKOH/g Sulfur ≈200 ppm Tin <.5 ppm

Blown soy oil typically contains a hydroxyl value of about 100-180 andmore typically about 160, while unblown soy oil typically has a hydroxylvalue of about 30-40. The infrared spectrum scans of two samples of thetype of blown soy oil used in the present invention are shown in FIGS. 1and 2. Blown soy oil and transesterified soy oil produced according tothe present invention have been found to have a glass transition atabout −137° C. to about −120° C. depending on the saccharide componentused and whether one is used at all. The glass transition measures thefirst signs of molecular movement in the polymer at certaintemperatures. The glass transition can be measured using a DynamicMechanical Thermal (DMT) analysis machine. Rheometric Scientific is onemanufacturer of DMT machines useful with the present invention.Applicants specifically utilize a DMTA5 machine from RheometricScientific. Other vegetable oils may also be used in the presentinvention. Typically, these other vegetable oils, which may also beblown vegetable oils, include rapeseed oil, cottonseed oil, palm oil,safflower oil, and canola oil; however, one of ordinary skill may beaware of other suitable bio-based polyols that will function within thebroad concepts of the present invention.

Except for the use of the bio-based polyol replacing the petroleum basedpolyol, the preferred B-side reactant used to produce urethane foam isgenerally known in the art. Accordingly, preferred blowing agents, whichmay be used for the invention, are those that are likewise known in theart and may be chosen from the group comprising HCFC 134A, ahydrochlorofluorocarbon refrigerant available from Dow Chemical Co. ofMidland, Mich.; methyl isobutyl ketone (MIBK); acetone; ahydrofluorocarbon; cyclopentane; methylene chloride; any hydrocarbon;and water or mixtures thereof. Presently, a mixture of cyclopentane andwater is preferred. Another possible blowing agent is ethyl lactate,which is derived from soybeans and is bio-based. At present, water isthe preferred blowing agent when a blowing agent is used. The blowingagents, such as water, react with the isocyanate (NCO) groups, toproduce a gaseous product. The concentrations of other reactants may beadjusted to accommodate the specific blowing agent used in the reaction.

As discussed above, when blown soy oil is used to prepare thetransesterified polyol of the B-side, the chain extender (cross-linkingagent) may be removed from the B-side of the urethane reactions andsimilar properties to urethane products produced using soy oil accordingto the teachings of WO 00/15684 and U.S. Pat. No. 6,180,686, thedisclosures of which are hereby incorporated by reference, are achieved.

If cross-linking agents are used in the urethane products of the presentinvention, they are also those that are well known in the art. They mustbe at least di-functional (a diol). The preferred cross-linking agentsfor the foam of the invention are ethylene glycol; 1,4 butanediol;diethanol amines; ethanol amines; tripropylene glycol, however, otherdiols and triols or greater functional alcohols may be used. It has beenfound that a mixture of tripropylene glycol; 1,4 butanediol; anddiethanol amines are particularly advantageous in the practice of thepresent invention. Dipropylene glycol may also be used as across-linking agent. Proper mixture of the cross-linking agents cancreate engineered urethane products of almost any desired structuralcharacteristics.

In addition to the B-side's vegetable oil, the optional blowingagent(s), and optional cross-linking agents, one or more catalysts maybe present. The preferred catalysts for the urethanes of the presentinvention are those that are generally known in the art and are mostpreferably tertiary amines chosen from the group comprising DABCO 33-LV®comprised of 33% 1,4-diazabicyclooctane (triethylenediamine) and 67%dipropylene glycol, a gel catalyst available from the Air ProductsCorporation; DABCO® BL-22 blowing catalyst available from the AirProducts Corporation; POLYCAT® 41 trimerization catalyst available fromthe Air Products Corporation; Dibutyltin dilaurate; Dibutyltindiacetate; stannous octane; Air Products' DBU® (1,8 Diazabicyclo [5.4.0]dibutyltin dilaurate); and Air Products' DBU® (1,8 Diazabicyclo [5.4.0]dibutyltin diacetate). Other amine catalysts, including any metalcatalysts, may also be used and are known by those of ordinary skill inthe art.

Also as known in the art, when forming foam urethane products, theB-side reactant may further comprise a silicone surfactant whichfunctions to influence liquid surface tension and thereby influence thesize of the bubbles formed and ultimately the size of the hardened voidcells in a final urethane foam product. This can effect foam density andfoam rebound (index of elasticity of foam). Also, the surfactant mayfunction as a cell-opening agent to cause larger cells to be formed inthe foam. This results in uniform foam density, increased rebound, and asofter foam.

A molecular sieve may further be present to absorb excess water from thereaction mixture. The preferred molecular sieve of the present inventionis available under the trade name L-paste™.

The urethane materials (products) of the present invention are producedby combining the A-side reactant with the B-side reactant in the samemanner as is generally known in the art. Advantageously, use of thepolyols of the present invention to replace the petroleum based polyoldoes not require significant changes in the method of performing thereaction procedure. Upon combination of the A and B side reactants, anexothermic reaction ensues that may reach completion in anywhere from afew seconds (approximately 2-4) to several hours or days depending onthe particular reactants and concentrations used. Typically, thereaction is carried out in a mold or allowed to free rise. Thecomponents may be combined in differing amounts to yield differingresults, as will be shown in the Examples presented below.

A petroleum based polyol such as polyether polyol (i.e., Bayercorporation's Multranol® 3901 polyether polyol and Multranol® 9151polyether polyol), polyester polyol, or polyurea polyol may besubstituted for some of the transesterified polyol in the B-side of thereaction, however, this is not necessary. Polyurea polyols areespecially useful to accelerate the curing time of the urethanematerials of the present invention when applied using an impingement mixspray applicator. This preferred B-side formulation is then combinedwith the A-side to produce a urethane material. The preferred A-side, asdiscussed previously, is comprised of methylenebisdiphenyl diisocyanate(MDI) or a prepolymer comprised of MDI and a vegetable oil, preferablysoy oil or a prepolymer of MDI and the transesterified polyol.

Flexible urethane foams may be produced with differing final qualitiesby not only regulating the properties of the transesterified polyol, butby using the same transesterified polyol and varying the particularother reactants chosen. For instance, it is expected that the use ofrelatively high molecular weight and high functionality isocyanates willresult in a less flexible foam than will use of a lower molecular weightand lower functionality isocyanate when used with the sametransesterified polyol. Likewise, as discussed earlier, the higher thefunctionality of the polyol produced by the transesterification process,the more rigid the foam produced using it will be. Moreover, it has beencontemplated that chain extenders may also be employed in the presentinvention. For example, butanediol, in addition to acting as across-linker, may act as a chain extender.

Urethane elastomers can be produced in much the same manner as urethanefoams. It has been discovered that useful urethane elastomers may beprepared using the transesterified polyol to replace some of or all ofthe petroleum based polyester or the polyether polyol. The preferredelastomer of the invention is produced using diphenylmethanediisocyanate (MDI) and the transesterified polyol. A catalyst may beadded to the reaction composition. The resulting elastomer has anapproximate density of about 52 lb. to about 75 lb. per cubic foot.

Applicants have also found that soybean oil and most other vegetableoils have C₃ and C₄ acid groups, which cause bitter smells when thevegetable polyols are reacted with isocyanates. In order to remove theseacid groups and the resultant odor from the end use product, Applicantshave also developed a way to effectively neutralize these lowering acidswith the functionality of the polyol.

Applicants blow nitrogen (N₂) through a solution of about 10% ammoniumhydroxide. Nitrogen gas was selected because it does not react with theammonium hydroxide. Any gas that does not react with the ammoniumhydroxide while still mixing the ammonium hydroxide through thevegetable oil would be acceptable. The ammonium hydroxide neutralizesacid groups that naturally occur in the vegetable oil. The pH oftransesterified, blown, and crude vegetable oil typically falls withinthe range of from about 5.9-6.2. Vegetable oil neutralized by theabove-identified process has a typical pH range of from about 6.5 toabout 7.2, but more typically from about 6.7 to 6.9. The removal ofthese C₃ and C₄ acid groups results in a substantial reduction in odorwhen the neutralized polyols are used to form isocyanates. For mostbio-based urethane applications of the present invention, the vegetableoil is typically neutralized prior to further modification to thevegetable oil to increase or decrease its functionality. Neutralizationof the vegetable oil is not required to carry out any of the methods ofthe present invention.

The following examples are the preparation of polyols of the presentinvention, as well as foams and elastomers of the invention formed usingthe transesterified polyol. The examples will illustrate variousembodiments of the invention. The A-side material in the followingexamples is comprised of modified diphenylmethane diisocyanate (MDI),unless otherwise indicated; however, any isocyanate compound could beused.

Also, “cure,” if used in the following examples, refers to the final,cured urethane product taken from the mold. The soy oil used in thefollowing examples is blown soy oil. Catalysts used include “DABCO33-LV®,” comprised of 33% 1,4-diazabicyclooctane and 67% dipropyleneglycol available from the Air Products Urethanes Division; “DABCO®BL-22,” a tertiary amine blowing catalyst also available from the AirProducts Urethanes Division; “POLYCAT® 41” (m, n′, n″,dimethylamino-propyl-hexahydrotriazine tertiary amine) also availablefrom the Air Products Urethanes Division; dibutyltin dilaurate (T-12);dibutyltin diacetate (T-1); and Air Products DBU® (1,8 Diazabicyclo[5.4.0]). The structures of the Air Products DBU®'s (1,8 Diazabicyclo[5.4.0]) used in the present invention are shown in FIG. 4.

A blowing catalyst in the following examples effects the timing of theactivation of the blowing agent. Some of the examples may include“L-paste™,” which is a trade name for a molecular sieve for absorbingwater. Some may also contain “DABCO® DC-5160” or “Air Products DC193®”,both are silicone surfactants available from Air Products UrethaneDivision.

EXAMPLES

All percentages referred to in the following examples refer to weightpercent, unless otherwise noted:

Example 1

Transesterification 2.5% Glycerin 5.0% Sorbitol 92.5% Polyurea polyoland Blown soy oil mixture Elastomer Formation B-side: 97 gTransesterified polyol formed above Air Products DBU ® = urethanecatalyst (1,8 Diazabicyclo [5.4.0]) 3% Butanediol (cross-linker) A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 55 parts A-side to100 parts B-side.

Example 2

Transesterification  2.5% Glycerin  5.0% Sorbitol 92.5% Polyurea polyoland Blown soy oil Elastomer Formation B-side:   97% Transesterifiedpolyol formed above Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0])   3% Dipropylene glycol (chain extender) A-sideModified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 46 parts A-side to100 parts B-side.

Example 3

Transesterification  2.5% Glycerin  5.0% Sorbitol 92.5% Blown soy oilElastomer Formation B-side:   97% Transesterified polyol formed aboveAir Products DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0])   3%Dipropylene glycol A-side Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 4

Transesterification  5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oilElastomer Formation B-side:   97% Transesterified polyol formed aboveAir Products DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0])   3%Dipropylene glycol A-side Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 5

Transesterification 10.0% Glycerin 20.0% Sorbitol 70.0% Blown soy oilElastomer Formation B-side: Transesterified polyol formed above AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0]) 3.0 gDipropylene glycol A-side Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 6

Transesterification 12.0% Glycerin 24.0% Sorbitol 12.0% Polyurea polyol52.0% Blown soy oil Elastomer Formation B-side: Transesterified polyolformed above Heat (190° F.) was used to catalyze the reaction Butanediol(cross-linker) A-side Modified monomeric MDI (Mondur ® MA-2903)

Example 7

Transesterification  5.0% Glycerin 10.0% Sorbitol   85% Polyurea polyoland Blown soy oil mixture Elastomer Formation B-side: 40.0 gTransesterified polyol formed above 0.3 g Air Products DBU ® = urethanecatalyst (1,8 Diazabicyclo [5.4.0]) 10.0 g Polyether polyol (BayerMultranol ® 9151) 3.0 g Dipropylene glycol A-side: Modified monomericMDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 38 parts A-side to100 parts B-side.

Example 8

Transesterification  5.0% Glycerin 10.0% Sorbitol   85% Polyurea polyoland Blown soy oil mixture Elastomer Formation B-side: 30.0 gTransesterified polyol formed above 20.0 g Polyether polyol (BayerMultranol ® 9151) 3.0 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0]) 3.0 g Dipropylene glycol A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 31 parts A-side to100 parts B-side.

Example 9

Transesterification  5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oilElastomer Formation B-side: 50.0 g Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0])3.0 g Dipropylene glycol A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 60 parts A-side to100 parts B-side.

Example 10

Transesterification  5.0% Glycerin 10.0% Sorbitol  5.0% Polyurea polyol80.0% Blown soy oil Elastomer Formation B-side: 40.0 g Transesterifiedpolyol formed above 0.4 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0]) 2.4 g Dipropylene glycol A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 11

Transesterification  5.0% Glycerin 10.0% Sorbitol  5.0% Polyurea polyol80.0% Blown soy oil Elastomer Formation B-side: 40.0 g Transesterifiedpolyol formed above 0.4 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0]) 2.4 g Dipropylene glycol A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 100 parts A-sideto 100 parts B-side.

Example 12

Transesterification  5.0% Glycerin 10.0% Sorbitol 12.0% Polyurea polyol73.0% Blown soy oil Elastomer Formation B-side: 50.0 g Transesterifiedpolyol formed above 0.4 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0]) 3.0 g Dipropylene glycol A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and cured at a temperature of 162° F.

Example 13

Transesterification  5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oilElastomer Formation B-side: 50.0 g Transesterified polyol formed above0.4 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0])3.0 g Dipropylene glycol A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 80 parts A-side to100 parts B-side and cured at a temperature of 166° F.

Example 14

Transesterification  5.0% Glycerin 10.0% Sorbitol 85.0% Blown soy oilElastomer Formation B-side: 50.0 g Transesterified polyol formed above0.4 g Dibutyltin diacetate (T-1) - catalyst 3.0 g Dipropylene glycolA-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and cured at a temperature of 153° F.

Example 15

Transesterification 1.0% (6.66 g) Glycerin 3.0% (13.4 g) Sorbitol 400.0g Blown soy oil

This mixture was heated at 196° F. for 1.5 hours.

Example 16

20.0 g of Glycerin heated and stirred at 178° F.

Introduced 40.0 g sorbitol slowly for about 4 minutes

Stayed milky until about 15 minute mark

At temperatures above 120° F., the solution was very fluid and clear. Attemperatures under 120° F., the solution was clear; however, it was veryviscous.

Added this mixture to 200.0 g of blown soy oil

200.0 g of blown soy oil heated to 178° F.

Introduced sorbitol, glycerin mixture as follows:

Added 10.0 g turned very cloudy within 30 seconds. Could not see thebottom of the beaker

-   -   Still very cloudy after 5 minutes and added 10.0 g    -   Viscosity increased and had to reduce paddle speed after 10        minutes    -   Viscosity reduced somewhat after about 18 minutes    -   A further reduction in viscosity after about 21 minutes

This was mixed in a 500 ML beaker with a magnetic paddle. The scientistswere not able to see through the beaker. After about 21 minutes, avortex appended in the surface indicating a further reduction inviscosity. At this time, the mixture lightened by a visible amount.Maintained heat and removed.

Reacted the new polyol with Modified Monomeric MDI, NCO-19.

New Polyol  100% DBU 0.03% MDI 50 p to 100 p of about Polyol Reaction:Cream time about 30 seconds Tack free in about 45 seconds Good physicalproperties after about 2 minutes

The reaction looked good, the material showed no signs of blow andseemed to be a good elastomer. It does however exhibit some signs of toomuch cross-linking and did not have the amount of elongation that wouldbe optimal.

A comparative reaction run along side with the un-modified blown soy oilwas not tack free at 24 hours.

Example 17

Transesterification  1.0% Glycerin  3.0% Sorbitol 96.0% Blown soy oilElastomer Formation B-side: 50.0 g Transesterified polyol formed as inExample 15 0.5 g Dibutyltin diacetate (T1) - catalyst 3.0 g Dipropyleneglycol A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and cured at a temperature of 154° F. for 4 minutes.

Example 18

B-side: 50.0 g Transesterified polyol formed from 20 g DipropyleneGlycol, 5 g Glycerin, and 20 g sorbitol blended with 200 g blown soy oil0.3 g Air Products DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0])A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 19

Transesterification 750 g Blown soy oil 150 g Glycerin  75 g Cane sugar

Example 20

B-side: 40.0 g Transesterified polyol formed as in Example 19 10.0 gPolyether polyol (Bayer Multranol ® 9151) 1.5 g Dipropylene Glycol 1.5 gButanediol 0.6 g Dibutyltin diacetate A-side: Modified monomeric MDI(Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 57 parts A-side to100 parts B-side and was set up on 20 seconds.

Example 21

B-side: 50.0 g Transesterified polyol formed as in Example 19 10.0 gPolyether polyol (Bayer Multranol ® 9151) 1.5 g Dipropylene Glycol 1.5 gButanediol 0.6 g Dibutyltin diacetate (T1) A-side: Modified monomericMDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 71 parts A-side to100 parts B-side.

Example 22

B-side: 40.0 g Transesterified polyol formed as in Example 19 10.0 gPolyether polyol (Bayer Multranol ® 9151) 1.5 g Dipropylene Glycol 1.5 gButanediol 0.6 g Dibutyltin diacetate (T1) A-side: Modified monomericMDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side.

Example 23

B-side: 100.0 g Transesterified polyol formed as in Example 19 20.0 gPolyether polyol (Bayer Multranol ® 9151) 3.0 g Dipropylene Glycol 3.0 gButanediol 0.7 g Dibutyltin diacetate (T1) 228.6 calcium carbonatefiller A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 25 parts A-side to100 parts B-side.

Example 24

B-side: 20.0 g Transesterified polyol formed as in Example 19 5.0 gTransesterification from Example 25 0.6 g Dipropylene Glycol 0.7 g AirProducts DBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0]) A-side:Modified monomeric MDI (Mondur ® MA-2903).

The B-side was combined with the A-side in a ratio of 57 parts A-side to100 parts B-side and was set up on 20 seconds.

Example 25

Transesterification 100 g Blown soy oil 27 g 63% glycerin and 37% canesugar reaction product mixture

The above was heated at a temperature of 230° F. and mixed for 15minutes.

Example 26

Transesterification 100.0 g Blown soy oil 13.5 g 63% glycerin and 37%cane sugar reaction product mixture

The above was heated at a temperature of 220° F.

Example 27

Transesterification 400 g Blown soy oil 12 g 33% Glycerin and 66%Sorbitol

The glycerin and sorbitol product was preheated to 195° F. The totalmixture was heated for 15 minutes at 202° F.

Example 28

B-side: 50.0 g Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 0.5 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 134° F. for 4 minutes.

Example 29

B-side: 50.0 g Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 0.8 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 67 parts A-side to100 parts B-side.

Example 30

B-side: 50.0 g Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 1.5 g Water 0.8 g Dibutyltin diacetate (T1) -catalyst A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 90 parts A-side to100 parts B-side.

Example 31

B-side: 50.0 g Transesterified polyol formed as in Example 27 3.0 gDipropylene glycol 1.5 g Water 0.8 g Dibutyltin diacetate (T1) -catalyst 0.2 g Silicon surfactant (Air Products ® DC193) A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side.

Example 32

B-side: 50.0 g Transesterified polyol formed as in Example 27  3.0 gDipropylene glycol  1.5 g Water  0.6 g Dibutyltin diacetate (T1) -catalyst  0.3 g Tertiary block amine catalyst A-side: Modified monomericMDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 74 parts A-side to100 parts B-side.

Example 33

B-side: 50.0 g Transesterified polyol formed as in Example 27  3.0 gDipropylene glycol  1.5 g Water  0.2 g Silicon surfactant (AirProducts ® DC193)  1.1 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 55 parts A-side to100 parts B-side.

Example 34

Transesterification: 50.0 g Blown soy oil  6.0 g 33% Glycerin and 66%Sorbitol reaction product mixture

Example 35

B-side: 50.0 g Transesterified polyol formed as in Example 34  3.0 gDipropylene glycol  0.6 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 148° F. for 3 minutes.

Example 36

Transesterification 20.0 g Glycerin 40.0 g Brown cane sugar

The above was heated at a temperature of 250° F. and mixed. 30 g of wetmass was recovered in a filter and removed.

Example 37

B-side: 50.0 g Transesterified polyol formed as in Example 36  3.0 gDipropylene glycol  1.0 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 67 parts A-side to100 parts B-side at a temperature of 171° F. for one minute.

Example 38

B-side: 50.0 g Transesterified polyol formed as in Example 36  3.0 gDipropylene glycol  1.0 g Dibutyltin diacetate (T1) - catalyst A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 67 parts A-side to100 parts B-side at a temperature of 146° F. for 1.5 minutes.

Example 39

B-side: 50.0 g Transesterified polyol formed as in Example 36  3.0 gDipropylene glycol  0.5 g Dibutyltin diacetate (T1) - catalyst A-side:Mondur ® MR light

The B-side was combined with the A-side in a ratio of 20 parts A-side to100 parts B-side at a temperature of 141° F. for 2 minutes.

Example 40

B-side: 50.0 g Transesterified polyol formed as in Example 36  3.0 gDipropylene glycol  1.0 g Dibutyltin diacetate (T1) - catalyst A-side:Mondur ® MR light

The B-side was combined with the A-side in a 1:1 ratio A-side to B-sideat a temperature of 152° F. and for 1 minute.

Example 41

Transesterification 350.0 g Blown soy oil  60.0 g Glycerin  35.0 g Whitecane sugar

The above was heated at a temperature of 240° F.

Example 42

B-side: 50.0 g Transesterified polyol formed as in Example 41 (preheatedto 101° F.)  3.0 g Dipropylene glycol  1.0 g Dibutyltin diacetate (T1) -catalyst A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 193° F. for 30 seconds.

Example 43

B-side: 50.0 g Transesterified polyol formed as in Example 42 (preheatedto 101° F.)  3.0 g Dipropylene glycol  0.8 g Dibutyltin diacetate (T1) -catalyst A-side: Mondur ® MR light

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side and reached a temperature of 227° F. for 20 seconds.

Example 44

Transesterification 35.9 g Glycerin  6.9 g Cane sugar 20.0 gTrimethylolpropane (preheated to 190° F.)

30 g of the above mixture was combined with 300 g of blown soy oil.

Example 45

Step 1 Heated 60 g trimethylolpropane (melting point of about 58° C.,about 136.4° F.) to liquid Step 2 Heated 30 g water and added 30 g canesugar Step 3 Added 60 g water and cane sugar to 60 g trimethylolpropaneand slowly raised the heat over 3 hours to 290° F. This drove off thewater.

Example 46

B-side: 20.0 g Transesterified polyol formed as in Example 44  0.5 gDibutyltin diacetate (T1) - catalyst A-side: Modified monomeric MDI(Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 47

Transesterification 1000 g Glycerin  500 g Cane sugar

The above was mixed at a temperature of 230° F. for 20 minutes.

Example 48

Transesterification:  22.3 g Reaction product formed as in Example 47100.0 g Blown soy oil

The above mixture was heated at a temperature of 227° F. for 20 minutes.

Example 49

50 g Water 50 g Cane sugar

The above was mixed and heated at a temperature of 85° F. for 20minutes.

Example 50

Transesterification  20 g Reaction mixture formed as in Example 53 100 gBlown soy oil

The above was heated at a temperature of 185° F. for 20 minutes, thenheated to a temperature of 250° F. for 80 minutes.

Example 51

B-side: 20.0 g Transesterified polyol formed as in Example 50  0.4 gDibutyltin diacetate (T1) - catalyst A-side: Mondur ® MR light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 52

B-side: 20.0 g Transesterified polyol formed as in Example 50  0.8 gDibutyltin diacetate (T1) - catalyst A-side: Mondur ® MR light

The B-side was combined with the A-side in a ratio of 54 parts A-side to100 parts B-side.

Example 53

Transesterification 3200 g Blown soy oil (5% sugar by volume)  48 g 67%Glycerin and 37% Cane sugar mixture

Example 54

B-side:  60.0 parts by weight Transesterified polyol formed as inExample 19  40.0 parts by weight Polyether Polyol (Bayer ® Multranol ®3901)  5.0 parts by weight Dipropylene Glycol  2.0 parts by weightDibutyltin diacetate (T1) - catalyst  2.1 parts by weight Water 109.0parts by weight Calcium Carbonate (filler) A-side: Mondur ® MR light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 55

B-side: 50.0 g Transesterified polyol formed as in Example 19  3.0 gDipropylene glycol  1.0 g Water  0.8 g Dibutyltin diacetate (T1) -catalyst 54.7 g Calcium Carbonate (filler) A-side: Bayer Corporation'sMondur ® MA-2901 (Isocyanate)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 56

B-side: 40.0 g Transesterified polyol formed as in Example 53 10.0 gPolyether polyol  1.5 g Dipropylene glycol  1.5 g Butanediol  1.0 gWater   55 g Calcium Carbonate (filler) A-side: Modified monomeric MDI(Mondur ® MA-2903)

Example 57

Transesterification 70.0 g Trimethylolpropane 33.0 g Pentaethertrol 60.0g Sugar

The above was heated to a temperature of 237° F. and added 15.0 g ofthis reaction product to 100.0 g of blown soy oil.

Example 58

B-side: 50.0 g Transesterified polyol formed as in Example 53  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 41 parts A-side to100 parts B-side at a temperature of 151° F. for 1 minute.

Example 59

B-side: 50.0 g Transesterified polyol formed as in Example 53  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 177° F. for 1 minute.

Example 60

B-side: 50.0 g Transesterified polyol formed as in Example 53  3.0 gDipropylene glycol  3.0 g Dibutyltin diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side at a temperature of 165° F. for 10 seconds.

Example 61

Transesterification 200 g Blown soy oil  20 g Trimethylolpropane

The above was heated to a temperature of 220° F. for 30 minutes.

Example 62

B-side: 50.0 g Transesterified polyol formed as in Example 61  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 168° F. for 35 seconds.

Example 63

Transesterification: 200 g Blown soy oil  20 g Trimethylolpropane

The above was heated at a temperature of 325° F. for 1 hour. Thetrimethyloipropane did not dissolve completely.

Example 64

B-side: 50.0 g Transesterified polyol formed as in Example 63  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 151° F. for 1 minute.

Example 65

Transesterification 100.0 g Blown soy oil  5.9 g Trimethylolpropane

The above was heated at a temperature of 235° F.

Example 66

B-side: 50.0 g Transesterified polyol formed as in Example 65  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 162° F. for 1 minute.

Example 67

B-side: 50.0 g Transesterified polyol formed as in Example 65  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 166° F. for 1 minute.

Example 68

Transesterification 2000 g Blown soy oil  100 g Trimethylolpropane

The above was heated at a temperature of 200° F. for 2 hours.

Example 69

B-side: 50.0 g Transesterified polyol formed as in Example 68  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The above was heated at a temperature of 166° F. for 1 minute.

Example 70

B-side: 50.0 g Transesterified polyol formed as in Example 68  4.0 gDipropylene Glycol  1.4 g Dibutyltin Diacetate (T1)  1.3 g Water A-side:Modified monomeric MDI (Mondur ® MA-2903)

Example 71

B-side: 50.0 g Transesterified polyol formed as in Example 68  3.0 gDipropylene Glycol  1.0 g Dibutyltin Diacetate (T1) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 61 parts A-side to100 parts B-side at a temperature of 172° F. for 1 minute.

Example 72

B-side: 50.0 g Transesterified polyol formed as in Example 68  2.0 gDibutyltin diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The above was heated at a temperature of 135° F.

Example 73

Transesterification 200.0 g Blown soy oil  4.0 g Trimethylolpropane

The above was heated at a temperature of 205° F.

Example 74

B-side: 50.0 g Transesterified polyol formed as in Example 73  2.0 gDibutyltin diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side at a temperature of 126° F.

Example 75

Transesterification 400 g Blown soy oil  62 g 66.7% Glycerin and 33.3%cane sugar mixture

The above mixture was heated at an average temperature of 205° F.

Example 76

B-side: 40.0 g Transesterified polyol formed as in Example 53  1.5 gDipropylene Glycol  1.5 g Butanediol  0.4 g Dibutyltin Diacetate (T1)10.0 g Polyether Polyol (Bayer Multranol ® 3901) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 77

B-side: 40.0 g Transesterified polyol formed as in Example 53 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1) 10.0g Polyether Polyol (Bayer Multranol ® 9151) A-side: Modified monomericMDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 78

B-side: 40.0 g Transesterified polyol formed as in Example 75 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1)A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 79

B-side: 20.0 g Transesterified polyol formed as in Example 75 0.4 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 80

B-side: 100.0 g Transesterified polyol formed as in Example 75 2.9 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 44 parts A-side to100 parts B-side.

Example 81

Transesterification 350 g Blown soy oil 52 g 66.7% Glycerin and 33.3%cane sugar mixture

The above was heated at a temperature of 194° F. for 4 hours.

Example 82

B-side: 40.0 g Transesterified polyol formed as in Example 53 1.5 gDipropylene Glycol 1.5 g Butanediol 0.3 g Dibutyltin Diacetate (T1) 10.0g Polyether Polyol (Bayer ® Multranol ® 3901) 97.0 g Calcium Carbonate(filler) A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 83

B-side: 20.0 g Transesterified polyol formed as in Example 53 1.5 gDipropylene Glycol 1.5 g Butanediol 0.4 g Dibutyltin Diacetate (T1) 0.4g Dibutyltin Dilaurate (T12) 8.0 g Polyether Polyol (Bayer ® Multranol ®3901) A-side: Mondur ® MR Light

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 84

Transesterification 400.0 g Blown soy oil 6.0 g Vinegar (to add acidicproton); hydrogen chloride may also be added 60.0 g 66.7% Glycerin and33.3% Cane sugar mixture

The above was heated at a temperature of 210° F. for 1 hour.

Example 85

B-side: 40.0 g Transesterified polyol formed as in Example 84 0.8 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 86

B-side: 40.0 g Transesterified polyol formed as in Example 84 0.8 gDibutyltin Diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 87

Transesterification First step: 80.0 g 66.7% Glycerin and 33.3% Canesugar 0.8 g Vinegar

The above was heated at a temperature of 260° F. for 30 minutes.

Second Step:

-   -   60 g of the above reaction product was reacted with 400 g blown        soy oil and mixed for 30 minutes.

Example 88

B-side: 50.0 g Transesterified polyol formed as in Example 87 1.0 gDibutyltin diacetate (T1) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 89

B-side: 20.0 g Transesterified polyol formed as in Example 87 0.5 gDibutyltin diacetate (T1) 20.0 g Bayer ® Multranol ® A-side: Mondur ® MRLight

The B-side was combined with the A-side in a ratio of 92 parts A-side to100 parts B-side at a temperature of 240° F. for 20 seconds.

Example 90

B-side: 50.0 g Blown soy oil 1.7 g Dibutyltin diacetate (T1) A-side:Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side.

Example 91

Transesterification 50.0 g Blown soy oil 100.0 g Bayer ® Multranol ®9185

The above was heated to a temperature of 100° F. for 5 hours.

Example 92

B-side: 50.0 g Transesterified polyol formed as in Example 91  0.7 gDibutyltin diacetate (T1) A-side: Mondur ® MR Light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 93

Transesterification 80.0 g Blown soy oil 20.0 g Polyether Polyol Bayer ®Multranol® 3901

The above was heated to a temperature of 100° C.

Example 94

B-side: 50.0 g Blown soy oil  0.8 g Dibutyltin Dilaurate (T12)  5.0 gButanediol A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 64 parts A-side to100 parts B-side at a temperature of 167° F. for 90 seconds.

Example 95

B-side: 50.0 g Blown soy oil 15.0 g Butanediol  0.8 g DibutyltinDilaurate (T12) A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 131 parts A-sideto 100 parts B-side at a temperature of 224° F. for 20 seconds.

Example 96

2000 g Transesterified polyol formed as in Example 80   6 g Dipropyleneglycol   6 g Butanediol  40 g Polyether Polyol (Bayer® Multranol ® 3901)

Example 97

B-side: 50.0 g Transesterified prepolymer polyol formed as in Example 96 0.3 g Dibutyltin Dilaurate (T12) A-side: Modified monomeric MDI(Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side for 120 seconds.

Example 98

B-side: 50.0 g Transesterified prepolymer polyol formed as in Example 96 0.2 g Dibutyltin Dilaurate (T12) A-side: Modified monomeric MDI(Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side for 160 seconds.

Example 99

B-side: 50.0 g Transesterified prepolymer polyol formed as in Example 96 0.4 g Dibutyltin Dilaurate (T12) A-side: Modified monomeric MDI(Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side for 80 seconds.

Example 100

B-side: 40.0 g Transesterified prepolymer polyol formed as in Example 96 0.2 g Dibutyltin Dilaurate (T12) A-side: Mondur ® MR Light mixed with15% blown soy oil for 120 seconds.

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 101

Transesterification 400 g Blown soy oil  60 g 66.7% Glycerin and 33%Cane sugar mixture

The above was heated at a temperature of 198° F. for 5 hours.

Example 102

B-side: 50.0 g Transesterified polyol formed as in Example 101  0.8 gDibutyltin Dilaurate (T12) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 42 parts A-side to100 parts B-side at a temperature of 149° F. for 260 seconds.

Example 103

B-side: 40.0 g Transesterified polyol formed as in Example 81  0.9 gDibutyltin Dilaurate (T12) 10.0 g Bayer ® Multranol ® A-side: Mondur ®MR Light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side at a temperature of 189° F. for 190 seconds.

Example 104

B-side: 40.0 g Transesterified polyol formed as in Example 81  3.0 gButanediol  0.9 g Dibutyltin Dilaurate (T12) 10.0 g Bayer ® Multranol ®A-side: Mondur ® MR Light

The above was heated at a temperature of 220° F. for 116 seconds.

Example 105

Transesterification 400 g Blown soy oil  60 g 66.7% Glycerin and 33.3%Cane Sugar

Example 106

B-side: 50.0 g Transesterified polyol formed as in Example 81  0.8 gDibutyltin Dilaurate (T12) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 107

B-side: 50.0 g Transesterified polyol formed as in Example 101  0.9 gDibutyltin Dilaurate (T12) A-side: Modified monomeric MDI (Mondur ®MA-2903)

The B-side was combined with the A-side in a ratio of 14 parts A-side to100 parts B-side.

Example 108

Transesterification 200.0 g Blown soy oil  14.3 g Honey

The above was heated at a temperature of 200° F. for 3 hours.

Example 109

B-side: 50.0 g Transesterified polyol formed as in Example 81  0.1 gDibutyltin Dilaurate (T12) 10.0 g Polyether Polyol (Bayer ® Multranol ®3901)  1.5 g Dipropylene glycol  1.5 g Butanediol A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 110

B-side: 40.0 g Transesterified polyol formed as in Example 81  0.2 gDibutyltin Dilaurate (T12) 10.0 g Polyether Polyol (Bayer ® Multranol ®3901)  1.5 g Dipropylene glycol  1.5 g Butanediol  0.2 g Air ProductsDBU ® = urethane catalyst (1,8 Diazabicyclo [5.4.0]) A-side: Modifiedmonomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 111

B-side: 80.0 g Transesterified polyol formed as in Example 81 20.0 gPolyether Polyol (Bayer ® Multranol ® 3901)  3.0 g Dipropylene glycol 3.0 g Butanediol  0.4 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0]) A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 112

B-side: 80.0 g Transesterified polyol formed as in Example 81 20.0 gPolyether Polyol (Bayer ® Multranol ® 3901)  3.0 g Dipropylene glycol 3.0 g Butanediol  0.6 g Air Products DBU ® = urethane catalyst (1,8Diazabicyclo [5.4.0]) A-side: Modified monomeric MDI (Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 113

B-side: 50.0 g Transesterified polyol formed as in Example 81  0.8 gDibutyltin Dilaurate (T12) 10.0 g Polyether Polyol (Bayer ® Multranol ®3901) 62.0 g Calcium Carbonate filler A-side: Mondur ® MR Light

The B-side was combined with the A-side in a ratio of 56 parts A-side to100 parts B-side.

Example 114

B-side: 50.0 g Transesterified polyol formed as in Example 81 0.2 gDibutyltin Dilaurate (T12) 0.2 g Air Products DBU ® = urethane catalyst(1,8 Diazabicyclo [5.4.0]) A-side: 20% Modified monomeric MDI (Mondur ®MA-2903) 80% Mondur ® MR Light

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 115

Transesterification 389.0 g Blown soy oil  13.0 g Dipropylene glycol 31.6 g Polyether Polyol (Bayer ® Multranol ® 3901) 381.5 g DibutyltinDilaurate (T12)

Example 116

B-side: 40.0 g Transesterified polyol formed as in Example 81 10.0 gPolyether Polyol (Bayer ® Multranol ® 9196)  0.4 g Dibutyltin Dilaurate(T12) A-side: 20.0 g Modified monomeric MDI (Mondur ® MA-2903) 80.0 gMondur ® MR Light

The B-side was combined with the A-side in a ratio of 82 parts A-side to100 parts B-side.

Example 117

B-side: 40.0 g Transesterified polyol formed as in Example 101  0.1 gDibutyltin Dilaurate (T12)  1.5 g Dipropylene glycol 10.0 g PolyetherPolyol (Bayer ® Multranol ® 3901)  0.4 g Air Products DBU ® = urethanecatalyst (1,8 Diazabicyclo [5.4.0]) A-side: Modified monomeric MDI(Mondur ® MA-2903)

The B-side was combined with the A-side in a ratio of 72 parts A-side to100 parts B-side.

Example 118

B-side: 50.0 g Transesterified polyol formed as in Example 81 0.5 gDibutyltin Dilaurate (T12) 2.0 g Butanediol 20.0 g Polyether Polyol(Bayer ® Multranol ® 9196) A-side: 20% Modified monomeric MDI (Mondur ®MA-2903) 80% Mondur ® MR Light

The B-side was combined with the A-side in a ratio of 88 parts A-side to100 parts B-side.

Example 119

B-side: 50.0 g Transesterified polyol formed as in Example 81 20.0 gPolyether Polyol (Bayer ® Multranol ® 9196)  0.5 g Dibutyltin Dilaurate(T12)  2.0 g Dipropylene Glycol A-side:   20 g Modified monomeric MDI(Mondur ® MA-2903)   80 g Mondur ® MR Light

Example 120 Water Blown TDI Seating-Type Foam

B-side: 50.0 g Transesterified blown soy oil 50.0 g Conventional polyol(3 Functional, 28 OH, 6000 Molecular weight, 1100 viscosity)  0.8 gNon-acid blocked Dibutyltin dilaurate catalyst  0.8 g Flexible blowingcatalyst (Bis(N,N, dimethylaminoethyl)ether),  1.0 g Flexible foamsilicon surfactant  1.0 g Water A-side: 2,4-Toluene Diisocyanate (TDI)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 121 Hydrocarbon Blown TDI Seating-Type Foam

B-side: 50.0 g Transesterified blown soy oil 50.0 g Conventional polyol(3 Functional, 28 OH, 6000 Molecular weight, 1100 viscosity)  0.8 gNon-acid blocked Dibutyltin Dilaurate catalyst  0.8 g Flexible blowingcatalyst (Bis(N,N,dimethylaminoethyl)ether)  1.0 g Flexible foamsilicone surfactant  4.0 g Cyclopentane, or other suitable blowingagents A-side: 2,4-Toluene Diisocyanate (TDI)

The B-side was combined with the A-side in a ratio of 40 parts A-side to100 parts B-side.

Example 122 Water Blown MDI Seating-Type Foam

B-side: 100.0 g Transesterified blown soy oil  1.0 g Flexible foamsurfactant  1.6 g Non-acid blocked Dibutyltin Dilaurate catalyst  3.0 gWater A-side: 100% Isocyanate terminated PPG (polypropylene etherglycol) Prepolymer (19% NCO, 400 Viscosity, 221 Equivalent weight, 2Functional)

The B-side was combined with the A-side in a ratio of 65 parts A-side to100 parts B-side.

Example 123 Hydrocarbon Blown MDI Seating-Type Foam

B-side: 100.0 g Transesterified blown soy oil  1.0 g Flexible foamsurfactant  1.6 g Non-acid blocked Dibutyltin Dilaurate catalyst  6.0 gCyclopentane, or other suitable blowing agent A-side: 100% Isocyanateterminated PPG (polypropylene ether glycol) Prepolymer (19% NCO, 400Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 65 parts A-side to100 parts B-side.

Example 124 Water Blown Higher Rebound MDI Searing-Type Foam

B-side: 50.0 g Transesterified blown soy oil 50.0 g Conventional polyol(3-functional, 28 OH, 6000 molecular weight, 1100 viscosity)  1.0 gFlexible foam surfactant  0.3 g Non-acid blocked Dibutyltin Dilauratecatalyst  0.4 g Non-acid blocked Alkyltin mercaptide catalyst  3.0 gWater A-side: 100% Isocyanate terminated PPG (polypropylene etherglycol) Prepolymer (19% NCO, 400 Viscosity, 221 Equivalent weight, 2Functional)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 125 Hydrocarbon Blown Higher Rebound MDI Searing-Type Foam

B-side: 50.0 g Transesterified blown soy oil 50.0 g Conventional polyol(3 Functional, 28 OH, 6000 Molecular weight, 1100 Viscosity)  1.0 gFlexible foam surfactant  0.3 g Non-acid blocked Dibutyltin Dilauratecatalyst  0.4 g Non-acid blocked Alkyltin mercaptide catalyst  6.0 gCyclopentane, or other suitable blowing agents A-side: 100% Isocyanateterminated PPG (polypropylene ether glycol) Prepolymer (19% NCO, 400Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 62 parts A-side to100 parts B-side.

Example 126 Water Blown Lightweight Rigid Urethane Material

B-side: 50.0 g Transesterified blown soy oil  1.2 g Non-acid blockedDibutyltin Dilaurate catalyst  1.0 g Water A-side: 100% Polymeric MDI(Methylenebisdipenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 127 Hydrocarbon Blown Lightweight Rigid Urethane Material

B-side: 100.0 g Transesterified blown soy oil  1.2 g Non-acid blockedDibutyltin Dilaurate catalyst  3.0 g Cyclopentane, or other suitableblowing agents A-side: 100% Polymeric MDI (Methylenebisdipenyldiisocyanate) (31.9% NCO, 200 Viscosity, 132 Equivalent weight, 2.8Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 128 Dense Rigid Urethane Material

B-side: 100.0 g Transesterified blown soy oil  1.2 g Non-acid blockedDibutyltin Dilaurate catalyst A-side: 100% Polymeric MDI(Methylenebisdipenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 129 Very Dense Rigid Urethane Material

B-side: 100.0 g Transesterified blown soy oil  1.2 g Non-acid blockedDibutyltin Dilaurate catalyst A-side: 100% Polymeric MDI(Methylenebisdipenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 110 parts A-sideto 100 parts B-side.

Example 130 Semi-Flexible Carpet Backing Material

B-side: 80.0 g Transesterified blown soy oil 20.0 g Conventional polyol(2 Functional, 28 OH, 4000 Molecular weight, 820 Viscosity)  0.2 gNon-acid blocked Dibutyltin Dilaurate catalyst  0.5 g Non-acid blockedAlkyltin mercaptide catalyst  4.0 g Dipropylene glycol A-side: 100%Monomeric MDI (methylenebisdiphenyl diisocyanate) (23% NCO, 500Viscosity, 183 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 45 parts A-side to100 parts B-side.

Example 131 Semi-Flexible Carpet Backing Material

B-side: 80.0 g Blown soy oil 20.0 g Conventional polyol (2 Functional,28 OH, 4000 Molecular weight, 820 Viscosity)  0.2 g Non-acid blockedDibutyltin Dilaurate catalyst  0.5 g Non-acid blocked Alkyltinmercaptide catalyst  4.0 g Dipropylene glycol A-side: 50% 4,4-MDI(methylenebisdiphenyl diisocyanate) Isocyanate 50% 2,4-MDI(methylenebisdiphenyl diisocyanate)Isocyanate mixture (33.6% NCO, 10Viscosity, 125 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 34 parts A-side to100 parts B-side.

Example 132 Flexible Carpet Padding Material

B-side: 85.0 g  Transesterified blown soy oil 7.5 g Conventional polyol(3 Functional, 28 OH, 4000 Molecular weight, 1100 Viscosity) 7.5 gConventional polyol (4 Functional, 395 OH, 568 Molecular weight, 8800Viscosity) 0.1 g Non-acid blocked Dibutyltin Dilaurate catalyst 0.2 gNon-acid blocked Alkyltin mercaptide catalyst 2.0 g Dipropylene glycolA-side: 100% Isocyanate terminated PPG (polypropylene ether glycol)Prepolymer (19% NCO, 400 Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side.

Example 133 Fast-Set Hard Skin Coating Material

B-side: 100.0 g   Transesterified blown soy oil 1.0 g Flexible foamsurfactant 0.8 g Non-acid blocked Dibutyltin Dilaurate catalyst 0.8 gFast acting Amicure DBU ® (Bicyclic Amidine) catalyst A-side: 100%Isocyanate terminated PPG (polypropylene ether glycol) Prepolymer (19%NCO, 400 Viscosity, 221 Equivalent weight, 2 Functional)

The B-side was combined with the A-side in a ratio of 68 parts A-side to100 parts B-side.

Example 134 Wood Molding Substitute Material

B-side: 100.0 g Transesterified blown soy oil  2.0 g Trimethylolpropane 1.0 g Non-acid blocked Dibutyltin Dilaurate catalyst A-side: 100%Polymeric MDI (methylenebisdiphenyl diisocyanate) (31.9% NCO, 200Viscosity, 132 Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 80 parts A-side to100 parts B-side.

Example 135 Semi-Rigid Floral Foam Type Material

B-side: 100.0 g  Transesterified blown soy oil 0.5 g Non-acid blockedDibutyltin Dilaurate catalyst 0.5 g Fast acting Amicure DBU (Bicyclicamidine) catalyst 5.0 g Water A-side: 100% Polymeric MDI(methylenebisdiphenyl diisocyanate) (31.9% NCO, 200 Viscosity, 132Equivalent weight, 2.8 Functional)

The B-side was combined with the A-side in a ratio of 70 parts A-side to100 parts B-side. A colorant (green) may be added if desired.

While vegetable oil based transesterified polyols are preferred inurethane production, an alternative embodiment of the present inventionincludes a cellular material that is the reaction product of an A-sideand a B-side, where the A-side is comprised of an isocyanate and theB-side comprises a vegetable oil, or a blown vegetable oil, across-linking agent comprised of a multi-functional alcohol, and acatalyst. This alternative further comprises a method for preparing acellular material comprising the reactive product of an A-side comprisedof a prepolymer diisocyanate and a B-side. The B-side comprises a firstvegetable oil, a cross-linking agent comprised of a multifunctionalalcohol, a catalyst, and optionally, a blowing agent.

There are several methods of application and production available forthe vegetable oil based polyurethanes of the present invention includingnon-transesterified vegetable oil based urethane transesterifiedvegetable oil based urethane, urethanes where a polyol is oxylated,and/or vegetable oil based urethanes where the vegetable oil has beenneutralized prior to reacting it in the B-side with the isocyanateA-side.

The A-side and B-side materials of the present invention are typicallymixed prior to application onto a substrate either via a static mixer ormore typically an impingement spray applicator. A static mixer orsimilar premixing device may be used to mix the A-side and B-side priorto application. As seen in FIG. 1, the preferred impingement spray gunapplicator 10 of the type used in connection with the method of thepresent invention includes a handle portion 12 having a grip 14, aprotecting portion 16 to protect the finger, and a trigger 18 that turnson the flow of A-side and B-side components. The spray gun applicator 10also includes an A-side intake 20, a B-side intake 22 and a nozzle spraygun applicator head 24 that includes an A-side outlet 21 and a B-sideoutlet 23, which in the preferred embodiment, are combined into a singlenozzle. Of course, separate external nozzles for each of the A-sideoutlet 21 and B-side outlet 23 can be advantageously employed. It ispossible, but not typical, for a bio-based urethane material of thepresent invention to be applied using two impingement spray applicatorswith focused spray patterns directed such that the A-side and B-sidereactants substantially mix prior to contacting the substrate material.

As shown in FIG. 2, the present invention further includes the method oflining a boat hull 26 (either the inside or outside) of a boat 25 with aurethane material of the present invention to create a composite. Suchlinings are typically for floatation, strength, sound absorption, andfire retardation where preferably incorporating fire retardant.

As shown in FIG. 3, the present invention further includes the method ofapplying a urethane material of the present invention to a vehicle 30 orvehicle component to create a composite, typically a vehicle cargo bay31, such as the truck bed shown. The urethane material of the presentinvention may be used to coat any part of a vehicle. An elastomerurethane material of the present invention, as is typical with mostcoatings of the present invention, is used when it is desired to protecta surface from the elements or from damage from debris of anysort—especially appropriate when the substrate to be coated with theurethane material is a vehicle cargo bed or the like. However, morecellular/foam type urethane material of the present invention can alsobe used according to the method of the present invention and istypically used when coating a material that requires sound damping orcushioning properties as in vehicle doors and other portions of vehicleswhere such properties are desired.

The typical formulation for a spray-on bedliner elastomer, whichApplicants currently believe will work on other substrates as wellincluding boat hulls and building materials includes the following:

Ingredient Amount (% w/w) B-side: about 2000 molecular weight about10% - about 15% Polyether amine polyol About 400 molecular weight about2% - about 5% Polyether amine polyol About 4800 molecular weight about8% - about 12% Polyether polyol Blown vegetable oil, about 12% - about18% Transesterified vegetable oil or other modified vegetable oil of thepresent invention cross-linker (when using blown about 5% - about 8% orcrude vegetable oil as typically utilized) surfactant (optional) about0.01% - about 1% Moisture Absorber (optional) about 0.01% - about 2%A-side: Isocyanate about 38% - about 45%

As shown in FIG. 4, another aspect of the present invention includesapplying a urethane material of the present invention to a buildingcomponent to create a composite, specifically shown in FIG. 4 is thecoating of a building roof 33, which is typically coated with anelastomeric/rigid urethane material. Any building or structuralcomponent may have any urethane material (either elastomeric/rigid or afoam) applied to it in accordance with the present invention as neededfor a given application. Wood, concrete, a metal such as steel, orasphalt may all be coated with the urethane material of the presentinvention. As seen in FIG. 5, a cellular or elastomeric/rigid urethanematerial of the present invention, although more typically a cellularmaterial, may be used to insulate or line a portion of the interior of abuilding structure 32 of a building 35. Of course, as appropriate, afire retardant is preferably included in the urethane material and alllocal building codes and customs should be followed.

As shown in FIGS. 6-7, any urethane material of the present inventionmay be employed advantageously to coat a carpet material 50 throughapplicator 56 to create a composite. When the carpet material 50 iscoated with a urethane material 52 of the present invention, a computercontrolled X-axis and Y-axis control system operated by computer 54 isused to control the position of the applicator fixture 38 or applicatorfixture 38 used to apply the urethane material relative to conveyor 36.While one impingement mix spray applicator fixture 38 is shown mountedto frame 40 (FIG. 6), two impingement mix spray applicator fixtures 38may also be used and directed such that the A-side and B-side reactantsmix prior to contacting the substrate (carpet material) surface (FIG.7). Conceivably, the urethane material could be manually applied to thecarpet backing, but there would be an increased chance that the urethanematerial would be of inconsistent thickness or too thin.

Using the present invention to apply a urethane material to the surfaceof a carpet material allows a small building to be used to apply carpetbacking to a carpet's griege goods whereas, in the prior art, muchlarger facilities with ovens as long as about 300 feet at temperaturesas high as 300° F. were required to apply conventional petroleum basedurethane materials as carpet backings to carpet materials. When polyureaor other similar compounds are added to the B-side of any of thebio-based urethane material of the present invention, the cure time isincreased such that the carpet backing urethane material applied inaccordance with the present invention allows the carpet material to berolled onto itself without damaging the carpeting material after onlyseconds. This allows for multiple X and Y axis computer controlledsystems to coat the carpet material much quicker and in a smaller space.

The use of the impingement mix spray applicators has the added benefitof forcing more urethane material into the carpet backing fibers, whichare essentially carpet fiber woven into or otherwise attached to aprimary backing material. This produces a carpet material where thetufts have superior pull strength (the tufts are more firmly held inplace) because more of the urethane material is forced into contact withthe tufts and the primary backing material, a greater mechanical andchemical bond is made between the tufts and the primary backing, whichholds the tufts in position.

Applicants currently believe that, to date, no one has used animpingement mix spray applicator or applicators to apply, not only abio-based urethane material (transesterified, unmodified, blown,oxylated, or neutralized vegetable oil) as disclosed herein, but that noone has used this method to apply a conventional petroleum basedurethane system to a carpet material as well. In the conventionalpetroleum based systems, as discussed herein, the A-side is the same asin the case of a bio-based urethane material of the present invention,but the B-side comprises conventional petroleum based polyols such aspolyurea polyols, polyether polyols, and polyester polyols. The sameoptional agents such as blowing agents, surfactants, and the likediscussed herein are also optionally used in this system.

Additionally, Applicants currently believe that Bio-based urethanematerials may be produced according to the present invention and used inplace of conventional petroleum based polyols in every instance, in mostcases with significant cost savings and other advantages. Applicantshave specifically contemplated using any of the bio-based urethanematerials of the present invention for the following applications:Astroturf®, which is an artificial turf surface having an elasticunderlayer shock absorbing material made with rubber or like materialand a urethane binder; in injection molding; as furniture cushioningmaterial or padding or backing material; as slab stock for mattressesand in pillows; as packaging material; in any molded foam product; asmicro-cellular shoe soles, shoe liners, and shoe outers; as refrigeratorcabinet insulation or insulation for various appliances in need ofinsulation, typically either sound or temperature insulation; as floormats; as a coating for seeds; as an ingredient, in the case of thebio-based polyol, in paint, as a floor coating, as a bonding and fillingfor natural and synthetic wood products (these typically utilizearomatic isocyanates as an A-side reactant component), which providesbetter fireproofing for the wood material; and as tires for vehicles ormachines.

The above description is considered that of the preferred embodimentsonly. Modifications of the invention will occur to those skilled in theart and to those who make or use the invention. Therefore, it isunderstood that the embodiments shown in the drawings and describedabove are merely for illustrative purposes and not intended to limit thescope of the invention, which is defined by the following claims asinterpreted according to the principles of patent law, including thedoctrine of equivalents.

The invention claimed is:
 1. A method of applying a urethane material toa vehicle substrate comprising the steps of: providing a vehiclesubstrate; and applying a urethane material to the vehicle substratewherein the urethane material comprises the reaction product of anA-side comprising an isocyanate and a B-side comprising a blown soy oil,at least one polyol at least partially derived from petroleum, across-linker.
 2. The method of applying a urethane material to a vehiclesubstrate of claim 1, wherein the cross-linker comprises hydroxyl groupsand the molar ratio of the hydroxyl groups of the cross-linker tohydroxyl groups of the blown soy oil is at least 0.7:1.
 3. The method ofapplying a urethane material to a vehicle substrate of claim 2, whereinthe B-side further comprises a blowing agent.
 4. The method of applyinga urethane material to a vehicle substrate of claim 3, wherein theblowing agent comprises at least one blowing agent chosen from the groupconsisting of a hydrochlorofluorocarbon, a hydrofluorocarbon, ahydrocarbon, water, and methylene chloride.
 5. The method of applying aurethane material to a vehicle substrate of claim 1, wherein the B-sidefurther comprises a blowing agent.
 6. The method of applying a urethanematerial to a vehicle substrate of claim 5, wherein the B-side furthercomprises a surfactant.
 7. The method of applying a urethane material toa vehicle substrate of claim 1, wherein the B-side further comprises asurfactant and a moisture absorber.
 8. The method of applying a urethanematerial to a vehicle substrate of claim 1, wherein the cross-linkercomprises a multifunctional alcohol in an amount of from about 5% toabout 8% by weight of the total of A-side and B-side.
 9. The method ofapplying a urethane material to a vehicle substrate of claim 1, whereinthe vehicle substrate is chosen from the group consisting of a vehiclecargo bay and a boat hull and wherein the urethane material is anelastomeric urethane material.
 10. The method of applying a urethanematerial to a vehicle substrate of claim 9, wherein the vehiclesubstrate is a vehicle cargo bay and the vehicle cargo bay is a truckbed having a truck bed surface and the elastomeric urethane materialprotects the truck bed surface from both the elements and any damagefrom debris.
 11. The method of applying a urethane material to a vehiclesubstrate of claim 1, wherein the vehicle substrate is chosen from thegroup consisting of a vehicle cargo bay; a boat hull; and a vehicle doorand wherein the urethane material in the vehicle door provides sounddampening properties to the door.
 12. The method of applying a urethanematerial to a vehicle substrate of claim 1, wherein the B-Side comprisesa plurality of polyols at least partially derived from petroleum and theplurality of polyols at least partially derived from petroleum include afirst polyether amine polyol in an amount of from about 10% to about 15%by weight of the total A-side and B-side and a second polyether aminepolyol in an amount of from about 2% to about 5% by weight of the totalA-side and B-side and wherein the molecular weight of the firstpolyether amine polyol is greater than the molecular weight of thesecond polyether amine polyol.
 13. The method of applying a urethanematerial to a vehicle substrate of claim 12, wherein the blown soy oilis present in an amount of from about 12% to about 18% by weight of thetotal A-side and B-side.
 14. The method of applying a urethane materialto a vehicle substrate of claim 13, wherein the plurality of polyols atleast partially derived from petroleum further comprises a polyetherpolyol that is different from the first polyether amine polyol and thesecond polyether amine polyol and wherein the polyether polyol ispresent in an amount of from about 8% to about 12% by weight of thetotal A-side and B-side and wherein the cross-linker is present in anamount of from about 5% to about 8% by weight of the total A-side andB-side.
 15. The method of applying a urethane material to a vehiclesubstrate of claim 14, wherein the molecular weight of the firstpolyether amine polyol is about 2000, the molecular weight of the secondpolyether amine polyol is about 400 and the molecular weight of thepolyether polyol is about
 4800. 16. The method of applying a urethanematerial to a vehicle substrate of claim 15, wherein the step ofapplying the urethane material comprises using an impingement spray gunapplicator having a separate A-side outlet and B-side outlet to applythe A-side and B-side simultaneously to the vehicle substrate.
 17. Themethod of applying a urethane material to a vehicle substrate of claim1, wherein the step of applying the urethane material comprises using animpingement spray gun applicator having a separate A-side outlet andB-side outlet to apply the A-side and B-side simultaneously to thevehicle substrate via the A-side outlet and B-side outlet.
 18. Themethod of applying a urethane material to a vehicle substrate of claim14, wherein the B-side further comprises a catalyst and wherein the stepof applying the urethane material comprises using an impingement spraygun applicator having a separate A-side outlet and B-side outlet toapply the A-side and B-side simultaneously to the vehicle substrate viathe A-side outlet and B-side outlet.
 19. The method of applying aurethane material to a vehicle substrate of claim 1, wherein the B-sidefurther comprises a catalyst.
 20. The method of claim 19, wherein theB-side comprises a non-acid blocked dibutyltin dilaurate catalyst and anon-acid blocked alkyltin mercaptide catalyst.